JP2023131909A - Liquid detergent composition - Google Patents
Liquid detergent composition Download PDFInfo
- Publication number
- JP2023131909A JP2023131909A JP2022036921A JP2022036921A JP2023131909A JP 2023131909 A JP2023131909 A JP 2023131909A JP 2022036921 A JP2022036921 A JP 2022036921A JP 2022036921 A JP2022036921 A JP 2022036921A JP 2023131909 A JP2023131909 A JP 2023131909A
- Authority
- JP
- Japan
- Prior art keywords
- component
- less
- mass
- salt
- cleaning composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000007788 liquid Substances 0.000 title claims abstract description 88
- 239000003599 detergent Substances 0.000 title claims abstract description 42
- 102000004190 Enzymes Human genes 0.000 claims abstract description 37
- 108090000790 Enzymes Proteins 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004382 Amylase Substances 0.000 claims abstract description 29
- 108010065511 Amylases Proteins 0.000 claims abstract description 29
- 102000013142 Amylases Human genes 0.000 claims abstract description 29
- 235000019418 amylase Nutrition 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 108091005804 Peptidases Proteins 0.000 claims abstract description 26
- 239000004365 Protease Substances 0.000 claims abstract description 25
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims abstract description 25
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 6
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 75
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkali metal salt Chemical class 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 7
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 7
- 239000001639 calcium acetate Substances 0.000 claims description 7
- 235000011092 calcium acetate Nutrition 0.000 claims description 7
- 229960005147 calcium acetate Drugs 0.000 claims description 7
- 229940051250 hexylene glycol Drugs 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229960005150 glycerol Drugs 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002920 sorbitol Drugs 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 40
- 230000000694 effects Effects 0.000 description 32
- 239000011550 stock solution Substances 0.000 description 27
- 238000003860 storage Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- 230000000977 initiatory effect Effects 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 229920002472 Starch Polymers 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 235000019698 starch Nutrition 0.000 description 10
- 239000008107 starch Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012459 cleaning agent Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000018102 proteins Nutrition 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000011148 calcium chloride Nutrition 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 108010020132 microbial serine proteinases Proteins 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229940100486 rice starch Drugs 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000021186 dishes Nutrition 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 108010075550 termamyl Proteins 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000013345 egg yolk Nutrition 0.000 description 2
- 210000002969 egg yolk Anatomy 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010200 folin Substances 0.000 description 2
- UBLXEEBHYISRFM-UHFFFAOYSA-M folin's reagent Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC(=O)C(=O)C2=C1 UBLXEEBHYISRFM-UHFFFAOYSA-M 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 230000006920 protein precipitation Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 2
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 2
- 229960004441 tyrosine Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UEFCKYIRXORTFI-UHFFFAOYSA-N 1,2-thiazolidin-3-one Chemical compound O=C1CCSN1 UEFCKYIRXORTFI-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 229940058012 1,3-dimethylol-5,5-dimethylhydantoin Drugs 0.000 description 1
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- IVQCQIORBPXQGP-UHFFFAOYSA-N 3-(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)NC(=O)N(CO)C1=O IVQCQIORBPXQGP-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- KQROHCSYOGBQGJ-UHFFFAOYSA-N 5-Hydroxytryptophol Chemical compound C1=C(O)C=C2C(CCO)=CNC2=C1 KQROHCSYOGBQGJ-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FVTVJVPAMICBAH-UHFFFAOYSA-N CC(C1C(=O)N(C(=O)N1C)Cl)Cl Chemical compound CC(C1C(=O)N(C(=O)N1C)Cl)Cl FVTVJVPAMICBAH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Enzymes And Modification Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、液体洗浄剤組成物に関する。具体的に本発明は、デンプン、タンパク質の汚れに対して優れた洗浄性を有し、かつ、原液、希釈液の何れにおいても酵素安定性に優れた液体洗浄剤組成物に関する。 FIELD OF THE INVENTION The present invention relates to liquid cleaning compositions. Specifically, the present invention relates to a liquid detergent composition that has excellent cleaning properties against starch and protein stains and has excellent enzyme stability in both undiluted and diluted solutions.
従来、学校、病院、社員食堂、給食施設等の大規模な調理施設では、食器類の下膳から洗浄までに時間を要するため、デンプンやタンパク質などの汚れが固着して除去し辛くなる。このため、自動食器洗浄機を用いて洗浄を行う前に食器類を酵素を含有する浸漬用洗浄剤に浸漬して、前洗いを行うことが一般的である。
前洗い用の浸漬液や前洗い後の自動食器洗浄中の洗浄液は組成物の原液を水で希釈した希釈液を用いることが一般的であるが、希釈液中では短時間で酵素安定性が失われ、浸漬又は洗浄時に酵素活性が低下してしまうという問題があった。
Traditionally, in large-scale cooking facilities such as schools, hospitals, company cafeterias, and school lunch facilities, it takes time to prepare and wash tableware, making it difficult to remove stains such as starch and protein. For this reason, before washing using an automatic dishwasher, tableware is generally pre-washed by immersing the tableware in a dipping detergent containing an enzyme.
The dipping solution for pre-washing and the cleaning solution for automatic dishwashing after pre-washing are generally diluted by diluting the undiluted solution of the composition with water. There was a problem that the enzyme activity was lost during soaking or washing.
従来の酵素を含む組成物としては、特許文献１には水、タンパク質分解酵素、アニオン界面活性剤もしくはノニオン界面活性剤、水分散性酸化防止剤、及び有機親水性水溶性ポリオールからなる酵素含有液状洗剤組成物が記載されている。特許文献２にはポリオキシエチレンポリオキシプロピレンアルキルエーテル、デンプン分解酵素、酵素安定化剤、可溶化剤、及びｐＨ調整剤を含有することを特徴とする前浸漬用洗浄剤組成物が記載されている。特許文献３には非イオン界面活性剤、芳香族スルホン酸又はその塩、多価アルコール、アミラーゼ、プロテアーゼを含有する中性洗浄剤組成物が記載されている。 As a conventional enzyme-containing composition, Patent Document 1 describes an enzyme-containing liquid composition consisting of water, a proteolytic enzyme, an anionic or nonionic surfactant, a water-dispersible antioxidant, and an organic hydrophilic water-soluble polyol. A detergent composition is described. Patent Document 2 describes a pre-soaking cleaning composition characterized by containing polyoxyethylene polyoxypropylene alkyl ether, an amylolytic enzyme, an enzyme stabilizer, a solubilizer, and a pH adjuster. There is. Patent Document 3 describes a neutral detergent composition containing a nonionic surfactant, aromatic sulfonic acid or its salt, polyhydric alcohol, amylase, and protease.
しかしながら、特許文献１～３に記載の洗浄剤組成物は何れも希釈液における酵素安定性が十分ではなかった。 However, all of the cleaning compositions described in Patent Documents 1 to 3 did not have sufficient enzyme stability in diluted solutions.
本発明は上記問題に鑑みなされたものである。即ち、本発明は、デンプン、タンパク質に対して優れた洗浄性を有し、原液、希釈液の何れにおいても優れた酵素安定性を示し、長期間酵素活性を維持できる液体洗浄剤組成物を提供することを目的とする。 The present invention has been made in view of the above problems. That is, the present invention provides a liquid detergent composition that has excellent detergency against starch and proteins, exhibits excellent enzyme stability in both undiluted solution and diluted solution, and can maintain enzyme activity for a long period of time. The purpose is to
そこで、本発明者は上記課題を解決するために鋭意検討を重ねた結果、アミラーゼ及びプロテアーゼを含む液体洗浄剤組成物において、芳香族スルホン酸又はその塩並びにチオ硫酸又はその塩、及び亜硫酸又はその塩からなる群より選択される少なくとも１種を、特定の割合で配合することにより、上記酵素の安定性が維持されることを見出した。 Therefore, as a result of extensive studies to solve the above problems, the present inventors have found that in a liquid cleaning composition containing amylase and protease, aromatic sulfonic acid or its salt, thiosulfuric acid or its salt, and sulfite or its salt are used. It has been found that the stability of the enzyme can be maintained by incorporating at least one salt selected from the group consisting of salts in a specific proportion.
即ち本発明は、
（１）（Ａ）成分として芳香族スルホン酸又はその塩、
（Ｂ）成分としてチオ硫酸又はその塩、及び亜硫酸又はその塩からなる群より選択される少なくとも一種、
（Ｃ）成分として多価アルコール、
（Ｄ）成分としてアミラーゼ、
（Ｅ）成分としてプロテアーゼ、
（Ｆ）成分として水、
を含有し、（Ａ）成分と（Ｂ）成分の質量比（Ａ）／（Ｂ）の値が４以上、１０００以下であり、組成物の２５℃におけるｐＨが６以上、８以下である液体洗浄剤組成物、
（２）（Ａ）成分が、キシレンスルホン酸又はその塩、トルエンスルホン酸又はその塩、及びクメンスルホン酸又はその塩からなる群より選択される少なくとも一種を含有する、（１）の液体洗浄剤組成物、
（３）（Ｃ）成分の多価アルコールが、エチレングリコール、プロピレングリコール、ブチレングリコール、ペンチレングリコール、ヘキシレングリコール、グリセリン、及びソルビトールからなる群より選択される少なくとも一種を含有する、（１）又は（２）の液体洗浄剤組成物、
（４）さらに、（Ｇ）成分としてギ酸又はそのアルカリ金属塩、塩化カルシウム、酢酸カルシウム、及びグリシンからなる群より選択される少なくとも一種以上の酵素安定化剤を含有する、（１）から（３）の何れかの液体洗浄剤組成物、
（５）さらに、（Ｈ）成分として下記の一般式（１）で表されるノニオン界面活性剤を含有する、（１）から（４）の何れかの液体洗浄剤組成物、
That is, the present invention
(1) Aromatic sulfonic acid or its salt as component (A),
(B) At least one member selected from the group consisting of thiosulfuric acid or its salt, and sulfite or its salt,
(C) polyhydric alcohol as a component;
(D) amylase as a component;
(E) protease as a component;
(F) water as a component;
, the mass ratio (A)/(B) of component (A) and component (B) is 4 or more and 1000 or less, and the pH of the composition at 25°C is 6 or more and 8 or less. cleaning composition,
(2) The liquid cleaning agent of (1), wherein component (A) contains at least one selected from the group consisting of xylene sulfonic acid or its salt, toluene sulfonic acid or its salt, and cumene sulfonic acid or its salt. Composition,
(3) The polyhydric alcohol of component (C) contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerin, and sorbitol (1) Or the liquid cleaning composition of (2),
(4) Furthermore, (G) contains at least one enzyme stabilizer selected from the group consisting of formic acid or an alkali metal salt thereof, calcium chloride, calcium acetate, and glycine, from (1) to (3). ) any liquid cleaning composition,
(5) The liquid cleaning composition according to any one of (1) to (4), further containing a nonionic surfactant represented by the following general formula (1) as the (H) component,
（式中、Ｒは、炭素数８以上、１６以下のアルキル基を表し、ｍは、２以上、１０以下の数を表し、ｎは、０以上、１０以下の数を表し、ｍ≧ｎである。）、及び
（６）自動食器洗浄機用洗浄剤又は食器の浸漬用洗浄剤として用いられる、（１）から（５）の何れかの液体洗浄剤組成物である。
(In the formula, R represents an alkyl group having 8 or more and 16 or less carbon atoms, m represents a number of 2 or more and 10 or less, n represents a number of 0 or more and 10 or less, and m≧n ), and (6) the liquid detergent composition according to any one of (1) to (5), which is used as a detergent for automatic dishwashers or a detergent for dipping dishes.
本発明の液体洗浄剤組成物は、デンプン、タンパク質に対する洗浄性に優れ、かつ、原液、希釈液の何れにおいても優れた酵素安定性を奏する。 The liquid detergent composition of the present invention has excellent detergency against starch and protein, and exhibits excellent enzyme stability in both the undiluted solution and the diluted solution.
本発明の液体洗浄剤組成物は、（Ａ）成分として芳香族スルホン酸又はその塩を含有する。ここでの芳香族スルホン酸としては、特に限定されないが、単環式又は二環式芳香族スルホン酸が好ましく、炭素数６以上、１１以下の単環式芳香族スルホン酸がより好ましく、炭素数７以上、９以下の単環式単環式芳香族スルホン酸がさらに好ましい。具体的に、芳香族スルホン酸として、キシレンスルホン酸、トルエンスルホン酸、クメンスルホン酸、ベンゼンスルホン酸、置換もしくは非置換ナフタレンスルホン酸等が挙げられる。 The liquid cleaning composition of the present invention contains aromatic sulfonic acid or a salt thereof as component (A). The aromatic sulfonic acid here is not particularly limited, but is preferably a monocyclic or bicyclic aromatic sulfonic acid, more preferably a monocyclic aromatic sulfonic acid having 6 or more carbon atoms and 11 or less carbon atoms. More preferred are monocyclic aromatic sulfonic acids of 7 or more and 9 or less. Specifically, aromatic sulfonic acids include xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, and the like.
これら芳香族スルホン酸の塩としては、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アンモニウム塩及びアルカノールアミン塩等が挙げられ、中でも酵素安定性の点からナトリウム塩、カリウム塩が好ましく、ナトリウム塩がより好ましい。
（Ａ）成分として、キシレンスルホン酸又はその塩、トルエンスルホン酸又はその塩、クメンスルホン酸又はその塩が好ましく、中でも貯蔵安定性の点からクメンスルホン酸塩がより好ましい。
なお、本発明の（Ａ）成分は、洗浄剤に一般的に使用されるアニオン界面活性剤と区別される。
Examples of the salts of these aromatic sulfonic acids include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, and alkanolamine salts, among which sodium salts and potassium salts are preferred from the viewpoint of enzyme stability, and sodium salts are preferred. is more preferable.
As component (A), xylene sulfonic acid or its salt, toluene sulfonic acid or its salt, and cumene sulfonic acid or its salt are preferable, and among them, cumene sulfonate is more preferable from the viewpoint of storage stability.
Note that component (A) of the present invention is distinguished from anionic surfactants commonly used in detergents.
これらは単独で用いても、二種以上を組み合わせてもよい。（Ａ）成分の配合量は特に制限されないが、貯蔵安定性、酵素安定性の点から、液体洗浄剤組成物の原液全量に対し、０．１質量％以上、８．０質量％以下が好ましく、０．５質量％以上、６．０質量％以下がより好ましく、１．０質量％以上、４．５質量％以下がさらに好ましい。（Ａ）成分の割合が０．１質量％未満であると貯蔵安定性が低下する場合があり、８．０質量％を超えると酵素安定性が低下する場合がある。 These may be used alone or in combination of two or more. The blending amount of component (A) is not particularly limited, but from the viewpoint of storage stability and enzyme stability, it is preferably 0.1% by mass or more and 8.0% by mass or less based on the total amount of the stock solution of the liquid cleaning composition. , more preferably 0.5% by mass or more and 6.0% by mass or less, and even more preferably 1.0% by mass or more and 4.5% by mass or less. If the proportion of component (A) is less than 0.1% by mass, storage stability may decrease, and if it exceeds 8.0% by mass, enzyme stability may decrease.
本発明の液体洗浄剤組成物は、（Ｂ）成分として、チオ硫酸又はその塩、及び亜硫酸又はその塩からなる群より選択される少なくとも一種を含有する。チオ硫酸の塩又は亜硫酸の塩として、ナトリウム塩、カリウム塩、アンモニウム塩等が挙げられる。
本発明の液体洗浄剤組成物の（Ｂ）成分として、チオ硫酸ナトリウム、チオ硫酸カリウム、亜硫酸ナトリウム、及び亜硫酸カリウムが好ましく、チオ硫酸ナトリウム及びチオ硫酸カリウムがより好ましい。
The liquid cleaning composition of the present invention contains, as component (B), at least one selected from the group consisting of thiosulfuric acid or a salt thereof, and sulfurous acid or a salt thereof. Examples of the thiosulfate salt or sulfite salt include sodium salt, potassium salt, ammonium salt, and the like.
As component (B) of the liquid detergent composition of the present invention, sodium thiosulfate, potassium thiosulfate, sodium sulfite, and potassium sulfite are preferable, and sodium thiosulfate and potassium thiosulfate are more preferable.
これらは単独で用いても、二種以上を組み合わせてもよい。（Ｂ）成分の配合量は特に制限されないが、貯蔵安定性、希釈時の酵素安定性の観点から、液体洗浄剤組成物の原液全量に対し、０．００５質量％以上、０．９質量％以下が好ましく、０．０１質量％以上、０．７質量％以下がより好ましく、０．０２質量％以上、０．５質量％以下がさらに好ましい。（Ｂ）成分の割合が０．００５質量％未満であると希釈液の酵素の安定性が低下する場合があり、０．９質量％を超えると貯蔵安定性が低下する場合がある。 These may be used alone or in combination of two or more. The blending amount of component (B) is not particularly limited, but from the viewpoint of storage stability and enzyme stability during dilution, 0.005% by mass or more and 0.9% by mass based on the total amount of the stock solution of the liquid cleaning composition. The following are preferable, 0.01 mass% or more and 0.7 mass% or less are more preferable, and 0.02 mass% or more and 0.5 mass% or less are still more preferable. If the ratio of component (B) is less than 0.005% by mass, the stability of the enzyme in the diluted solution may decrease, and if it exceeds 0.9% by mass, storage stability may decrease.
本発明の液体洗浄剤組成物は、（Ｃ）成分として多価アルコールを含有する。ここで使用する多価アルコールは、本発明の効果を奏する限り特に限定されないが、炭素数が２以上、４４以下、水酸基の数が２以上、１５以下である多価アルコールを使用することが好ましい。炭素数は、２以上、２０以下がより好ましく、２以上、１２以下がさらに好ましい。水酸基の数は、２以上、９以下がより好ましく、２以上、５以下がさらに好ましい。あるいは、（Ｃ）成分の多価アルコールとして、分子量が６０以上、１０００以下の化合物を使用することができ、分子量６０以上、５００以下が好ましく、６０以上、３００以下がより好ましい。 The liquid cleaning composition of the present invention contains polyhydric alcohol as component (C). The polyhydric alcohol used here is not particularly limited as long as it achieves the effects of the present invention, but it is preferable to use a polyhydric alcohol having 2 or more and 44 or less carbon atoms and 2 or more and 15 or less hydroxyl groups. . The number of carbon atoms is more preferably 2 or more and 20 or less, and even more preferably 2 or more and 12 or less. The number of hydroxyl groups is more preferably 2 or more and 9 or less, and even more preferably 2 or more and 5 or less. Alternatively, as the polyhydric alcohol of component (C), a compound having a molecular weight of 60 or more and 1000 or less can be used, preferably a molecular weight of 60 or more and 500 or less, and more preferably 60 or more and 300 or less.
（Ｃ）成分の多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、１，３－ブチレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、ヘキシレングリコール、グリセリン、ポリグリセリン、ソルビトール等が挙げられ、中でもエチレングリコール、プロピレングリコール、ブチレングリコール、ペンチレングリコール、ヘキシレングリコール、グリセリン、ソルビトールが好ましく、プロピレングリコール、ペンチレングリコール、ヘキシレングリコール、グリセリンがより好ましく、プロピレングリコールがさらに好ましい。 Examples of the polyhydric alcohol of component (C) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4- Examples include butanediol, 1,5-pentanediol, hexylene glycol, glycerin, polyglycerin, sorbitol, etc. Among them, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerin, and sorbitol are preferred, and propylene glycol, glycerin, and sorbitol are preferred. Glycol, pentylene glycol, hexylene glycol, and glycerin are more preferred, and propylene glycol is even more preferred.
これらは単独で用いても、二種以上を組み合わせてもよい。（Ｃ）成分の配合量は特に制限されないが、酵素安定性及び貯蔵安定性の観点から、液体洗浄剤組成物の原液全量に対し、１．０質量％以上、５０質量％以下が好ましく、１５質量％以上、４５質量％以下がより好ましく、２５質量％以上、４０質量％以下がさらに好ましい。（Ｃ）成分の割合が１質量％未満であると、原液及び希釈液の酵素の安定性が低下する場合があり、５０質量％を超えるとその配合割合に見合う効果は期待できない場合がある。 These may be used alone or in combination of two or more. The blending amount of component (C) is not particularly limited, but from the viewpoint of enzyme stability and storage stability, it is preferably 1.0% by mass or more and 50% by mass or less, based on the total amount of the stock solution of the liquid cleaning composition. It is more preferably 25% by mass or more and 40% by mass or less, and even more preferably 25% by mass or more and 40% by mass or less. If the proportion of component (C) is less than 1% by mass, the stability of the enzyme in the stock solution and diluted solution may decrease, and if it exceeds 50% by mass, an effect commensurate with the blending proportion may not be expected.
本発明の液体洗浄剤組成物は、（Ｄ）成分として、アミラーゼを含有する。（Ｄ）成分として使用するアミラーゼの至適ｐＨは、通常、６．０以上、８．０以下であり、好ましくは６．５以上、７．５以下である。また、至適温度は、通常、４０℃以上、７０℃以下、好ましくは５５℃以上、６５℃以下である。 The liquid detergent composition of the present invention contains amylase as component (D). The optimum pH of amylase used as component (D) is usually 6.0 or more and 8.0 or less, preferably 6.5 or more and 7.5 or less. Further, the optimum temperature is usually 40°C or higher and 70°C or lower, preferably 55°C or higher and 65°C or lower.
（Ｄ）成分のアミラーゼとしては、市販のアミラーゼ製剤を使用することができる。例えば、ノボザイムズ社製の商品名Ａｍｐｌｉｆｙ Ｐｒｉｍｅ １００Ｌ、Ｔｅｒｍａｍｙｌ ３００Ｌ、Ｔｅｒｍａｍｙｌ Ｕｌｔｒａ ３００Ｌ、Ｄｕｒａｍｙｌ １２０Ｔ、Ｄｕｒａｍｙｌ ３００Ｌ、Ｓｔａｉｎｚｙｍｅ １２Ｌ、Ｓｔａｉｎｚｙｍｅ Ｐｌｕｓ １２Ｌ、Ｓｔａｉｎｚｙｍｅ Ｐｌｕｓ Ｅｖｉｔｙ １２Ｌ、Ｄｕｐｏｎｔ社製のＰｒｅｆｅｒｅｎｚ Ｓ１１０、Ｐｒｅｆｅｒｅｎｚ Ｓ２１０などが挙げられる。 As the amylase component (D), commercially available amylase preparations can be used. For example, Novozymes' product names Amplify Prime 100L, Termamyl 300L, Termamyl Ultra 300L, Duramyl 120T, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, Stainzyme Plus Evity 12L, Preferenz S110, Preferenz S210 manufactured by DuPont, etc. .
これらは単独で用いても、二種以上を組み合わせてもよい。（Ｄ）成分の配合量は特に制限されないが、液体洗浄剤組成物の原液全量に対し、アミラーゼ純分で０．００１質量％以上、５．０質量％以下であることが好ましく、０．００３質量％以上、２．０質量％以下であることがより好ましく、０．００５質量％以上、１．０質量％以下であることがさらに好ましい。（Ｄ）成分の割合が、０．００１質量％未満であるとデンプン汚れに対する洗浄性が低下する場合があり、５．０質量％より多く配合してもそれに見合う効果が得られない場合がある。 These may be used alone or in combination of two or more. The blending amount of component (D) is not particularly limited, but it is preferably 0.001% by mass or more and 5.0% by mass or less in terms of pure amylase based on the total amount of the stock solution of the liquid cleaning composition, and 0.003% by mass or less. It is more preferably 0.005% by mass or more and 1.0% by mass or less, more preferably 0.005% by mass or more and 1.0% by mass or less. If the proportion of component (D) is less than 0.001% by mass, the detergency against starch stains may be reduced, and even if it is blended in an amount greater than 5.0% by mass, commensurate effects may not be obtained. .
本発明の液体洗浄剤組成物は、（Ｅ）成分として、プロテアーゼを含有する。（Ｅ）成分として使用するプロテアーゼの至適ｐＨは、通常、６．０以上、９．０以下であり、好ましくは６．５以上、８．０以下である。至適温度は、通常、４０℃以上、７０℃以下でで、好ましくは５５℃以上、６５℃以下である。 The liquid detergent composition of the present invention contains protease as component (E). The optimum pH of the protease used as component (E) is usually 6.0 or more and 9.0 or less, preferably 6.5 or more and 8.0 or less. The optimum temperature is usually 40°C or higher and 70°C or lower, preferably 55°C or higher and 65°C or lower.
（Ｅ）成分としては、市販のプロテアーゼ製剤を使用することができる。例えば、ノボザイムズ社製のＳａｖｉｎａｓｅ １６Ｌ、Ｓａｖｉｎａｓｅ Ｅｖｉｔｙ １６Ｌ、Ｓａｖｉｎａｓｅ Ｕｌｔｒａ １６Ｌ、Ｓａｖｉｎａｓｅ Ｕｌｔｒａ １６ＸＬ、Ｂｌａｚｅ Ｅｖｉｔｙ １６Ｌ、Ｅｖｅｒｌａｓｅ １６Ｌ ＴｙｐｅＥＸ、Ｅｖｅｒｌａｓｅ Ｕｌｔｒａ １６Ｌ、Ｅｓｐｅｒａｓｅ ８．０Ｌ、Ａｌｃａｌａｓｅ ２．５Ｌ、Ａｌｃａｌａｓｅ Ｕｌｔｒａ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ Ｕｌｔｒａ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ Ｕｌｔｒａ ２．５ＸＬ、Ｌｉｑｕａｎａｓｅ Ｅｖｉｔｙ ３．５Ｌ、Ｃｏｒｏｎａｓｅ ４８Ｌや、ＤｕＰｏｎｔ社製のＥｘｃｅｌｌｅｎｚ Ｐ１０００、Ｅｘｃｅｌｌｅｎｚ Ｐ１２５０、Ｅｆｆｅｃｔｅｎｚ Ｐ１００、Ｅｆｆｅｃｔｅｎｚ Ｐ１５０、Ｅｆｆｅｃｔｅｎｚ Ｐ２００、Ｅｆｆｅｃｔｅｎｚ Ｐ３０００、Ｐｒｅｆｅｒｅｎｚ Ｐ１００、Ｐｒｅｆｅｒｅｎｚ Ｐ２００、Ｐｒｅｆｅｒｅｎｚ Ｐ３００などが挙げられる。 As component (E), commercially available protease preparations can be used. For example, Savinase 16L, Savinase Evity 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Blaze Evity 16L, Everlase 16L TypeEX, Ever manufactured by Novozymes. lase Ultra 16L, Esperase 8.0L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Liquanase Evity 3.5L, Coronase 48L, Excellenz P1000 manufactured by DuPont, Excel lens P1250, Effectenz P100, Effectenz P150, Effectenz P200, Effectenz P3000, Preferenz P100 , Preferenz P200, Preferenz P300, etc.
これらは単独で用いても、二種以上を組み合わせてもよい。（Ｅ）成分の配合量は特に制限されないが、液体洗浄剤組成物の原液全量に対し、プロテアーゼ純分で０．００１質量％以上、５．０質量％以下であることが好ましく、０．００３質量％以上、２．０質量％以下であることがより好ましく、０．００５質量％以上、１．０質量％以下であることがさらに好ましい。（Ｅ）成分の割合が、０．００１質量％未満であるとタンパク質汚れに対する洗浄性が低下する場合があり、５．０質量％より大きくなると酵素安定性が低下する場合がある。 These may be used alone or in combination of two or more. The blending amount of component (E) is not particularly limited, but it is preferably 0.001% by mass or more and 5.0% by mass or less in terms of pure protease based on the total amount of the stock solution of the liquid cleaning composition, and 0.003% by mass or less. It is more preferably 0.005% by mass or more and 1.0% by mass or less, more preferably 0.005% by mass or more and 1.0% by mass or less. If the proportion of component (E) is less than 0.001% by mass, the detergency against protein stains may decrease, and if it exceeds 5.0% by mass, enzyme stability may decrease.
本発明の液体洗浄剤組成物では、（Ｆ）成分として、水を配合する。（Ｆ）成分としての水として、水道水、軟水化処理水、純水、ＲＯ水、イオン交換水、蒸留水を用いることができる。経済性の点から、水道水が好ましい。水道水としては、例えば、東京都荒川区の水道水（ｐＨ＝７．６、総アルカリ度（炭酸カルシウム換算として）４０．５ｍｇ／Ｌ、ドイツ硬度２．３°ＤＨ（そのうち、カルシウム硬度１．７°ＤＨ、マグネシウム硬度０．６°ＤＨ）、塩化物イオン２１．９ｍｇ／Ｌ、ナトリウム及びその化合物１５ｍｇ／Ｌ、硝酸態窒素及び亜硝酸態窒素１．２ｍｇ／Ｌ、フッ素及びその化合物０．１ｍｇ／Ｌ、ホウ素及びその化合物０．０４ｍｇ／Ｌ、総トリハロメタン０．０１６ｍｇ／Ｌ、残留塩素０．４ｍｇ／Ｌ、有機物（全有機炭素量）０．７ｍｇ／Ｌ）が挙げられる。水は、液体洗浄剤組成物全体が１００質量％となるように配合（必要に応じて後述する（Ｇ）成分、（Ｈ）成分及び任意成分を配合する場合、これらを含めて全体が１００質量％となるように配合）されるものである。 In the liquid detergent composition of the present invention, water is blended as component (F). As water as component (F), tap water, softened water, pure water, RO water, ion exchange water, and distilled water can be used. From an economic point of view, tap water is preferred. Examples of tap water include tap water from Arakawa Ward, Tokyo (pH = 7.6, total alkalinity (in terms of calcium carbonate) 40.5 mg/L, German hardness 2.3° DH (of which calcium hardness is 1.5 mg/L). 7°DH, magnesium hardness 0.6°DH), chloride ion 21.9mg/L, sodium and its compounds 15mg/L, nitrate nitrogen and nitrite nitrogen 1.2mg/L, fluorine and its compounds 0. 1 mg/L, boron and its compounds 0.04 mg/L, total trihalomethane 0.016 mg/L, residual chlorine 0.4 mg/L, and organic matter (total organic carbon amount) 0.7 mg/L). Water is blended so that the entire liquid detergent composition is 100% by mass (if necessary, the (G) component, (H) component, and optional components described later are blended, the total amount including these is 100% by mass). %).
本発明の液体洗浄剤組成物において、（Ａ）成分と（Ｂ）成分の質量比（Ａ）／（Ｂ）の値が４以上、１０００以下であることを要する。また、（Ａ）／（Ｂ）の値は、４以上、３００以下であることが好ましく、１０以上、１５０以下であることがより好ましい。
（Ａ）／（Ｂ）の値が４未満である場合は、貯蔵安定性が悪くなる場合がある。また、（Ａ）／（Ｂ）の値が１０００よりも大きいと、本発明の液体洗浄剤組成物の原液及び希釈液における酵素安定性が悪くなる場合がある。
In the liquid cleaning composition of the present invention, the mass ratio (A)/(B) of the component (A) and the component (B) is required to be 4 or more and 1000 or less. Further, the value of (A)/(B) is preferably 4 or more and 300 or less, more preferably 10 or more and 150 or less.
If the value of (A)/(B) is less than 4, the storage stability may deteriorate. Moreover, when the value of (A)/(B) is larger than 1000, the enzyme stability in the stock solution and diluted solution of the liquid detergent composition of the present invention may deteriorate.
本発明の液体洗浄剤組成物では、さらに（Ｇ）成分として酵素安定化剤を含有することができる。（Ｇ）成分として、公知の酵素安定剤を使用することができ、特に限定されないが、例えば、塩化カルシウム、酢酸カルシウム、乳酸カルシウム、リン酸カルシウム、クエン酸カルシウム、グルコン酸カルシウム、硫酸カルシウム、水酸化カルシウム等のカルシウム化合物、ホウ酸又はそのアルカリ金属塩、ギ酸又はそのアルカリ金属塩、グリシン、リジン、ロイシン、バリン、アスパラギン酸、グルタミン酸等のアミノ酸が挙げられる。
これらの中でも、塩化カルシウム、酢酸カルシウム、ギ酸ナトリウム、グリシン、アスパラギン酸が好ましく、酢酸カルシウム、グリシン、ギ酸ナトリウムがより好ましい。
The liquid detergent composition of the present invention may further contain an enzyme stabilizer as component (G). As component (G), known enzyme stabilizers can be used, including but not limited to, calcium chloride, calcium acetate, calcium lactate, calcium phosphate, calcium citrate, calcium gluconate, calcium sulfate, and calcium hydroxide. Examples include calcium compounds such as boric acid or its alkali metal salts, formic acid or its alkali metal salts, and amino acids such as glycine, lysine, leucine, valine, aspartic acid, and glutamic acid.
Among these, calcium chloride, calcium acetate, sodium formate, glycine, and aspartic acid are preferred, and calcium acetate, glycine, and sodium formate are more preferred.
これらは単独で用いても、二種以上を組み合わせてもよい。（Ｇ）成分の配合量は特に制限されないが、液体洗浄剤組成物の原液全量に対し、０．００１質量％以上、５質量％以下であることが好ましく、０．００３質量％以上、４質量％以下であることがより好ましく、０．０１質量％以上、２質量％以下であることが特に好ましい。（Ｇ）成分の濃度が０．００１質量％未満であると、酵素安定化剤として十分に機能しない場合があり、５質量％より多く配合すると貯蔵安定性が低下する場合がある。 These may be used alone or in combination of two or more. The blending amount of component (G) is not particularly limited, but it is preferably 0.001% by mass or more and 5% by mass or less, and 0.003% by mass or more and 4% by mass based on the total amount of the stock solution of the liquid cleaning composition. % or less, and particularly preferably 0.01% by mass or more and 2% by mass or less. If the concentration of component (G) is less than 0.001% by mass, it may not function sufficiently as an enzyme stabilizer, and if it is blended in an amount greater than 5% by mass, storage stability may decrease.
本発明の液体洗浄剤組成物は、（Ｈ）成分として、下記の一般式（１）で表されるノニオン界面活性剤を含有することができる。 The liquid detergent composition of the present invention can contain a nonionic surfactant represented by the following general formula (1) as the component (H).
（式中、Ｒは、炭素数８以上、１６以下のアルキル基を表し、ｍは、２以上、１０以下の数を表し、ｎは、０以上、１０以下の数を表し、ｍ≧ｎである。） (In the formula, R represents an alkyl group having 8 or more and 16 or less carbon atoms, m represents a number of 2 or more and 10 or less, n represents a number of 0 or more and 10 or less, and m≧n be.)
一般式（１）において、Ｒは、炭素数８以上、１６以下のアルキル基を表す。アルキル基としては、飽和、不飽和、直鎖、分岐の何れのアルキル基でもよく、例えば、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基等の第１級アルキル基、第２級アルキル基が挙げられる。これらの中でも洗浄性と抑泡性の点から、Ｒは、炭素数１２～１４のアルキル基が好ましく、炭素数１２～１４の直鎖１級アルキル基がより好ましい。 In general formula (1), R represents an alkyl group having 8 or more and 16 or less carbon atoms. The alkyl group may be any saturated, unsaturated, straight chain, or branched alkyl group, such as octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Examples include primary alkyl groups and secondary alkyl groups such as. Among these, R is preferably an alkyl group having 12 to 14 carbon atoms, more preferably a linear primary alkyl group having 12 to 14 carbon atoms, from the viewpoint of detergency and foam suppressing properties.
一般式（１）において、ｍは、２以上、１０以下の数を表し、ｎは、０以上、１０以下の数を表す。ｍは、一般式（１）中のオキシエチレン基の平均付加モル数を表し、３以上、８以下の数であることが好ましい。ｎは、一般式（１）中のオキシプロピレン基の平均付加モル数を表し、１～６の数であることが好ましい。 In general formula (1), m represents a number of 2 or more and 10 or less, and n represents a number of 0 or more and 10 or less. m represents the average number of added moles of oxyethylene groups in general formula (1), and is preferably a number of 3 or more and 8 or less. n represents the average number of added moles of oxypropylene groups in general formula (1), and is preferably a number from 1 to 6.
本発明の液剤洗浄剤組成物は、（Ｈ）成分を単独で用いても、二種以上を組み合わせてもよい。（Ｈ）成分の配合量は特に制限されないが、油脂汚れに対する洗浄性と貯蔵安定性の観点から、液体洗浄剤組成物の原液全量に対し、０．１質量％以上、５．０質量％以下であることが好ましく、０．２質量％以上、４．０質量％以下であることがより好ましく、０．５質量％以上、３．０質量％以下であることがさらに好ましい。（Ｈ）成分の濃度が０．１質量％未満であると油脂汚れに対する洗浄性が低下する場合があり、５．０質量％を超えると貯蔵安定性が低下する場合がある。 In the liquid detergent composition of the present invention, the component (H) may be used alone or in combination of two or more. The blending amount of the component (H) is not particularly limited, but from the viewpoint of cleaning performance against oil and fat stains and storage stability, 0.1% by mass or more and 5.0% by mass or less based on the total amount of the stock solution of the liquid cleaning composition. It is preferably 0.2% by mass or more and 4.0% by mass or less, and even more preferably 0.5% by mass or more and 3.0% by mass or less. If the concentration of the component (H) is less than 0.1% by mass, the detergency against oil and fat stains may decrease, and if it exceeds 5.0% by mass, storage stability may decrease.
本発明の液体洗浄剤組成物のｐＨは、原液及び希釈液において、２５℃で６．０～８．０である。ｐＨが６未満もしくは８を超えると、原液及び希釈液において何れも酵素安定性が低下する。 The pH of the liquid detergent composition of the present invention is 6.0 to 8.0 at 25°C in the neat solution and the diluted solution. When the pH is less than 6 or more than 8, the enzyme stability decreases in both the undiluted solution and the diluted solution.
本発明の液体洗浄剤組成物のｐＨを調整するため、ｐＨ調整剤を使用することができる。ｐＨ調整剤としては、２５℃のｐＨが６未満の場合、例えば、水酸化ナトリウム、水酸化カリウム、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ，Ｎ－ジメチルプロパン－1，3－ジアミン等が挙げられ、好ましくは水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、モノエタノールアミン、モノイソプロパノールアミン等のアルカノールアミンが挙げられる。これらは単独でも２種以上を組み合わせてもよい。また、ｐＨが８を超える場合、塩酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、安息香酸、マロン酸、コハク酸、グルタル酸、アジピン酸、グルコン酸、エチレンジアミン四酢酸、ホスホノブタントリカルボン酸、リン酸などが挙げられるが、好ましくは、塩酸である。これらは単独でも２種以上を組み合わせてもよい。 A pH adjuster can be used to adjust the pH of the liquid cleaning composition of the present invention. As a pH adjuster, when the pH at 25°C is less than 6, for example, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N- Examples include methylethanolamine, N-methyldiethanolamine, N,N-dimethylpropane-1,3-diamine, and preferably alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, monoethanolamine, and monoisopropanolamine. Examples include alkanolamines such as These may be used alone or in combination of two or more. In addition, when the pH exceeds 8, hydrochloric acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, benzoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, ethylenediaminetetraacetic acid, phosphonobutane tricarboxylic acid, Examples include acids, phosphoric acid, etc., but hydrochloric acid is preferred. These may be used alone or in combination of two or more.
本発明の液体洗浄剤組成物には、本発明の効果を損なわない範囲で、必要に応じ当該技術分野で通常使用される他の成分を含有していてもよい。このような成分としては、高分子分散剤、増粘剤、殺菌剤、香料、色素等が挙げられる。 The liquid detergent composition of the present invention may contain other components commonly used in the technical field, as necessary, to the extent that the effects of the present invention are not impaired. Examples of such components include polymeric dispersants, thickeners, bactericidal agents, fragrances, pigments, and the like.
高分子分散剤としては、例えば、ポリアクリル酸、ポリマレイン酸、ポリメタクリル酸、アクリル酸型共重合体、マレイン酸型共重合体、メタクリル酸型共重合体、アクリル酸－スルホン酸型モノマー共重合体等が挙げられる。
高分子分散剤の配合量は特に限定されないが、液体洗浄剤組成物の原液全量に対し、０．０１質量％～１０質量％で配合させることが好ましい。
Examples of polymeric dispersants include polyacrylic acid, polymaleic acid, polymethacrylic acid, acrylic acid type copolymers, maleic acid type copolymers, methacrylic acid type copolymers, and acrylic acid-sulfonic acid type monomer copolymers. Examples include merging.
The amount of the polymer dispersant to be blended is not particularly limited, but it is preferably blended in an amount of 0.01% by mass to 10% by mass based on the total amount of the stock solution of the liquid cleaning composition.
増粘剤としては、カルボキシビニルポリマー、カルボキシメチルセルロース等が挙げられる。
増粘剤の配合量は特に限定されないが、液体洗浄剤組成物の原液全量に対し、０．０１質量％～１０質量％で配合させることが好ましい。
Examples of thickeners include carboxyvinyl polymers and carboxymethyl cellulose.
The amount of the thickener to be blended is not particularly limited, but it is preferably blended in an amount of 0.01% by mass to 10% by mass based on the total amount of the stock solution of the liquid cleaning composition.
殺菌剤としては、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、２－メチル－４－イソチアゾリン－３－オン、イソチアゾリン－３－オン、１，２－ベンズイソチアゾリン－３－オン、Ｎ－ｎ－ブチル－ベンズイソチアゾリン－３－オン等のチアゾリン類、１，３－ジメチロール－５，５－ジメチルヒダントイン、１又は３－モノメチロール－５，５－ジメチルヒダントイン、ジメチルヒダントイン、１、３－ジクロロ－５，５－ジメチルヒダントイン、１、３－ジクロロエチルメチルヒダントイン等のヒダントイン類、アルキルジメチルアンモニウムクロライド、アルキルジメチルベンジルアンモニウムクロライド、アルキルジメチルヒドロキシエチルアンモニウムクロライド、ベンゼトニウムクロライド等の四級アンモニウム塩等が挙げられる。
殺菌剤の配合量は特に限定されないが、液体洗浄剤組成物の原液全量に対し、０．００１質量％～５質量％で配合させることが好ましい。
As a fungicide, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Thiazolines such as Nn-butyl-benzisothiazolin-3-one, 1,3-dimethylol-5,5-dimethylhydantoin, 1 or 3-monomethylol-5,5-dimethylhydantoin, dimethylhydantoin, 1,3 - Hydantoins such as dichloro-5,5-dimethylhydantoin and 1,3-dichloroethylmethylhydantoin, quaternary ammonium salts such as alkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, alkyldimethylhydroxyethylammonium chloride, benzethonium chloride, etc. can be mentioned.
The amount of the disinfectant to be blended is not particularly limited, but it is preferably blended in an amount of 0.001% by mass to 5% by mass based on the total amount of the stock solution of the liquid cleaning composition.
香料としては、例えば、天然香料、合成香料、これらの調合香料等が挙げられる。
また、色素としては、例えば、天然色素、合成色素、又はこれらの混合物が挙げられる。
Examples of fragrances include natural fragrances, synthetic fragrances, mixed fragrances thereof, and the like.
Furthermore, examples of the pigment include natural pigments, synthetic pigments, and mixtures thereof.
本発明の液体洗浄剤組成物は、食器類の洗浄に使用することができる。
食器類として、皿、椀、コップ等の食器、包丁、鍋、フライパン、やかん、まな板等の調理器具、瓶、タッパー等の保存容器等が挙げられるがこれらに限定されない。
食器類の材質として、プラスチック類（シリコーン樹脂等も含む）、ガラス、金属、木等が挙げられるが、これらに限定されない。
The liquid cleaning composition of the present invention can be used for cleaning tableware.
Examples of tableware include, but are not limited to, tableware such as plates, bowls, and cups, cooking utensils such as knives, pots, frying pans, kettles, and cutting boards, and storage containers such as bottles and Tupperware.
Materials for tableware include, but are not limited to, plastics (including silicone resins, etc.), glass, metal, wood, and the like.
本発明の液体洗浄剤組成物を用いて食器類を洗浄する方法としては、特に限定されないが、例えば、（１）前記液体洗浄剤組成物の原液をスポンジなどの可撓性道具に、任意に水と共に含ませて、食器類表面に前記洗浄剤組成物を接触させて洗浄する方法、（２）上記液体洗浄剤組成物を水で希釈して浸漬液を作成し、そこに食器を浸漬し、一定時間経過後に前記食器をスポンジなどの可撓性材料を用いて浸漬液を水で洗い流すか、又は自動食器洗浄機で再度洗浄する方法、（３）前記液体洗浄剤組成物の原液を自動食器洗浄機に投入し、さらに水で希釈して、自動食器洗浄機にて食器類を洗浄する方法などが挙げられる。 The method for cleaning tableware using the liquid cleaning composition of the present invention is not particularly limited, but includes, for example: (1) applying the stock solution of the liquid cleaning composition to a flexible tool such as a sponge; (2) The liquid cleaning composition is diluted with water to create an immersion liquid, and the tableware is immersed therein. , after a certain period of time, the dishes are rinsed with water using a flexible material such as a sponge, or washed again in an automatic dishwasher; (3) automatic washing of the undiluted solution of the liquid cleaning composition; For example, the solution may be placed in a dishwasher, diluted with water, and then washed in an automatic dishwasher.
上記（２）又は（３）のように、本発明の液体洗浄剤組成物を水で希釈して使用する場合、液体洗浄剤組成物の原液の濃度が希釈液全量に対して、好ましくは０．０１質量％以上、より好ましくは０．０３質量％以上、そして、好ましくは１質量％以下、より好ましくは０．５質量％以下となるように調整する。 As in (2) or (3) above, when the liquid cleaning composition of the present invention is diluted with water and used, the concentration of the stock solution of the liquid cleaning composition is preferably 0 with respect to the total amount of the diluted liquid. The content is adjusted to .01% by mass or more, more preferably 0.03% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less.
本発明の液体洗浄剤組成物が原液であるとき、当該原液は、その全量に対して、（Ａ）成分を好ましくは０．１質量％以上、８．０質量％以下、より好ましくは０．５質量％以上、６．０質量％以下、さらに好ましくは１．０質量％以上、４．５質量％以下で含有し、（Ｂ）成分を好ましくは０．００５質量％以上、０．９質量％以下、より好ましくは０．０１質量％以上、０．７質量％以下、さらに好ましくは０．０２質量％以上、０．５質量％以下で含有し、（Ｃ）成分を好ましくは１．０質量％以上、５０質量％以下、より好ましくは１５質量％以上、４５質量％以下、さらに好ましくは、２５質量％以上、４０質量以下で含有し、（Ｄ）成分をアミラーゼ純分で好ましくは０．００１質量％以上、５．０質量％、より好ましくは０．００３質量％以上、２．０質量％、さらに好ましくは０．００５質量％以上、１．０質量％以下で含有し、（Ｅ）成分をプロテアーゼ純分で好ましくは０．００１質量％以上、５．０質量％以上、より好ましくは０．００３質量％以上、２．０質量％以下、さらに好ましくは０．００５質量％以上、１．０質量％以下で含有する。 When the liquid cleaning composition of the present invention is a stock solution, the stock solution preferably contains component (A) in an amount of 0.1% by mass or more and 8.0% by mass or less, more preferably 0.1% by mass or less, based on the total amount. Contains 5% by mass or more and 6.0% by mass or less, more preferably 1.0% by mass or more and 4.5% by mass or less, and contains component (B) preferably 0.005% by mass or more and 0.9% by mass. % or less, more preferably 0.01% by mass or more and 0.7% by mass or less, even more preferably 0.02% by mass or more and 0.5% by mass or less, and preferably contains component (C) at 1.0% by mass or less. The content of component (D) is preferably 0% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, even more preferably 25% by mass or more and 40% by mass or less, and the amylase pure content of component (D) is preferably 0. Contains at least .001% by mass and 5.0% by mass, more preferably at least 0.003% by mass and 2.0% by mass, even more preferably at least 0.005% by mass and at most 1.0% by mass, and (E ) component as a pure protease, preferably 0.001% by mass or more, 5.0% by mass or more, more preferably 0.003% by mass or more, 2.0% by mass or less, even more preferably 0.005% by mass or more, Contained at 1.0% by mass or less.
本発明の液体洗浄剤組成物が原液であるとき、当該原液は、その全量に対して、（Ｇ）成分を０．００１質量％以上、５質量％以下、好ましくは０．００３質量％以上、４質量％以下、より好ましくは０．０１質量％以上、２質量％以下で含有してもよい。
本発明の液体洗浄剤組成物が原液であるとき、当該原液は、その全量に対して、（Ｈ）成分を０．１質量％以上、５．０質量％以下、好ましくは０．２質量％以上、４．０質量％以下、より好ましくは０．５質量％以上、３．０質量％以下で含有することができる。
When the liquid cleaning composition of the present invention is a stock solution, the stock solution contains component (G) in an amount of 0.001% by mass or more and 5% by mass or less, preferably 0.003% by mass or more, based on the total amount of the liquid cleaning composition of the present invention. It may be contained in an amount of 4% by mass or less, more preferably 0.01% by mass or more and 2% by mass or less.
When the liquid cleaning composition of the present invention is a stock solution, the stock solution contains component (H) in an amount of 0.1% by mass or more and 5.0% by mass or less, preferably 0.2% by mass based on the total amount. It can be contained in an amount of 4.0% by mass or less, more preferably 0.5% by mass or more and 3.0% by mass or less.
上記（１）～（３）の方法で水は、本発明の液体洗浄剤組成物の（Ｆ）成分で使用する水と同様の水を用いることができ、水道水を用いることが好ましい。
上記（２）の方法における浸漬液の温度は、好ましくは６５℃未満、より好ましくは６０℃以下、さらに好ましくは５５℃以下、そして、好ましくは２５℃以上である。
食器類を浸漬させる時間は特に限定されないが、好ましくは１分以上、より好ましくは３分以上、さらに好ましくは５分以上であり、好ましくは１２時間以下、より好ましくは３時間以下、さらに好ましくは３０分以下である。
In the methods (1) to (3) above, water similar to the water used in component (F) of the liquid detergent composition of the present invention can be used, and tap water is preferably used.
The temperature of the immersion liquid in the method (2) above is preferably lower than 65°C, more preferably 60°C or lower, even more preferably 55°C or lower, and preferably 25°C or higher.
The time for soaking tableware is not particularly limited, but is preferably 1 minute or more, more preferably 3 minutes or more, even more preferably 5 minutes or more, and preferably 12 hours or less, more preferably 3 hours or less, and even more preferably It takes less than 30 minutes.
以下、本発明を実施例と比較例により具体的に説明する。実施例、比較例において配合に用いた各成分を下記に示す。なお、以下の実施例等において「％」は特に記載がない限り質量％を表し、表中における実施例及び比較例の配合の数値は純分の質量％を表す。実施例、比較例において使用した化合物を以下に記す。 Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Each component used in the formulation in Examples and Comparative Examples is shown below. In addition, in the following Examples and the like, "%" represents mass % unless otherwise specified, and the numerical values of the formulations of Examples and Comparative Examples in the table represent mass % of pure content. The compounds used in Examples and Comparative Examples are described below.
（Ａ）成分
Ａ－１：クメンスルホン酸ナトリウム
Ａ－２：キシレンスルホン酸ナトリウム
Ａ－３：パラトルエンスルホン酸ナトリウム
(A) Component A-1: Sodium cumene sulfonate A-2: Sodium xylene sulfonate A-3: Sodium paratoluene sulfonate
（Ｂ）成分
Ｂ－１：チオ硫酸ナトリウム
Ｂ－２：チオ硫酸カリウム
Ｂ－３：亜硫酸ナトリウム
(B) Component B-1: Sodium thiosulfate B-2: Potassium thiosulfate B-3: Sodium sulfite
（Ｂ）成分の比較成分
Ｂ′－１：ピロ亜硫酸ナトリウム
(B) Comparative component B'-1: Sodium pyrosulfite
（Ｃ）成分
Ｃ－１：プロピレングリコール
Ｃ－２：ヘキシレングリコール
Ｃ－３：グリセリン
(C) Component C-1: Propylene glycol C-2: Hexylene glycol C-3: Glycerin
（Ｄ）成分
Ｄ－１：アミラーゼ１（商品名：Ａｍｐｌｉｆｙ Ｐｒｉｍｅ １００Ｌ、ノボザイムズ社製）
Ｄ－２：アミラーゼ２（商品名：Ｐｒｅｆｅｒｅｎｚ Ｓ２１０、ＤｕＰｏｎｔ社製）
Ｄ－３：アミラーゼ３（商品名：Ｔｅｒｍａｍｙｌ Ｕｌｔｒａ ３００Ｌ、ノボザイムズ社製）
(D) Component D-1: Amylase 1 (product name: Amplify Prime 100L, manufactured by Novozymes)
D-2: Amylase 2 (product name: Preferenz S210, manufactured by DuPont)
D-3: Amylase 3 (trade name: Termamyl Ultra 300L, manufactured by Novozymes)
（Ｅ）成分
Ｅ－１：プロテアーゼ１（商品名：ＳａｖｉｎａｓｅＥｖｉｔｙ １６Ｌ、ノボザイムズ社製）
Ｅ－２：プロテアーゼ２（商品名：Ｅｘｃｅｌｌｅｎｚ Ｐ１２５０、ＤｕＰｏｎｔ社製）
Ｅ－３：プロテアーゼ３（商品名：Ｅｘｃｅｌｌｅｎｚ Ｐ１００、ＤｕＰｏｎｔ社製）
(E) Component E-1: Protease 1 (product name: SavinaseEvity 16L, manufactured by Novozymes)
E-2: Protease 2 (product name: Excellenz P1250, manufactured by DuPont)
E-3: Protease 3 (product name: Excellenz P100, manufactured by DuPont)
（Ｆ）成分
Ｆ－１：イオン交換水
(F) Component F-1: Ion exchange water
（Ｇ）成分
Ｇ－１：ギ酸ナトリウム
Ｇ－２：グリシン
Ｇ－３：酢酸カルシウム
(G) Component G-1: Sodium formate G-2: Glycine G-3: Calcium acetate
（Ｈ）成分
Ｈ－１：ポリオキシエチレン（ＥＯ８モル）ポリオキシプロピレン（ＰＯ３モル）ラウリルエーテル
Ｈ－２：ポリオキシエチレン（ＥＯ５モル）ポリオキシプロピレン（ＰＯ３モル）トリデシルエーテル
Ｈ－３：ポリオキシエチレン（ＥＯ３モル）ポリオキシプロピレン（ＰＯ３モル）トリデシルエーテル
(H) Component H-1: Polyoxyethylene (EO 8 mol) Polyoxypropylene (PO 3 mol) Lauryl ether H-2: Polyoxyethylene (EO 5 mol) Polyoxypropylene (PO 3 mol) Tridecyl ether H-3: Poly Oxyethylene (3 moles of EO) Polyoxypropylene (3 moles of PO) Tridecyl ether
（Ｉ）その他成分
Ｉ－１：グルコン酸ナトリウム
Ｉ－２：塩酸
Ｉ－３：トリエタノールアミン
(I) Other components I-1: Sodium gluconate I-2: Hydrochloric acid I-3: Triethanolamine
各実施例の組成物は、（Ｆ）成分の水を組成物の合計が１００質量％となるように混合槽に加え、次いで（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分（必要に応じて（Ｇ）成分、（Ｈ）成分、（Ｉ）成分）を混合槽中に配合し、十分に混合撹拌して調製した。 The composition of each example was prepared by adding water as component (F) to a mixing tank so that the total of the composition was 100% by mass, and then adding component (A), component (B), component (C), and component (D). ), component (E) (component (G), component (H), and component (I) as required) were blended in a mixing tank and thoroughly mixed and stirred.
実施例１～４０、比較例１～１０
表１～表５に示す液体洗浄剤組成物を調製した。各液体洗浄剤組成物を用いて、ｐＨ、洗浄性、酵素安定性、貯蔵安定性を測定した。表１～４に実施例１～４０の結果を、表５に比較例１～１０の結果をそれぞれ示す。
Examples 1 to 40, Comparative Examples 1 to 10
Liquid cleaning compositions shown in Tables 1 to 5 were prepared. Using each liquid detergent composition, pH, detergency, enzyme stability, and storage stability were measured. Tables 1 to 4 show the results of Examples 1 to 40, and Table 5 shows the results of Comparative Examples 1 to 10, respectively.
※１：ｐＨの測定方法
ｐＨメーター（ＨＯＲＩＢＡ製；ｐＨ／イオンメーターＦ－２３）にｐＨ測定用複合電極（ＨＯＲＩＢＡ製；ガラス摺り合わせスリーブ型）を接続し、電源を入れる。ｐＨ電極内部液としては、飽和塩化カリウム水溶液（３．３３ｍｏｌ／Ｌ）を使用した。
次に、ｐＨ４．０１標準液（フタル酸塩標準液）、ｐＨ６．８６（中性リン酸塩標準液）、ｐＨ９．１８標準液（ホウ酸塩標準液）をそれぞれ１００ｍＬビーカーに充填し、２５℃の恒温槽に３０分間浸漬した。恒温に調整された標準液にｐＨ測定用電極を３分間浸し、ｐＨ６．８６→ｐＨ９．１８→ｐＨ４．０１の順に校正操作を行った。
各液体洗浄剤組成物を１００ｍＬビーカーに充填し、恒温槽内にて２５℃に調整した。恒温に調整された試料にｐＨ測定用電極を３分間浸し、ｐＨを測定した。
なお、下記の表は、液体洗浄剤組成物の原液のｐＨの値を示す。
*1: How to measure pH Connect a composite electrode for pH measurement (manufactured by HORIBA; glass rubbed sleeve type) to a pH meter (manufactured by HORIBA; pH/ion meter F-23) and turn on the power. A saturated aqueous potassium chloride solution (3.33 mol/L) was used as the pH electrode internal solution.
Next, fill a 100 mL beaker with each of pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), It was immersed in a constant temperature bath at ℃ for 30 minutes. The pH measuring electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and a calibration operation was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.
A 100 mL beaker was filled with each liquid cleaning composition, and the temperature was adjusted to 25° C. in a constant temperature bath. A pH measurement electrode was immersed in a sample whose temperature was adjusted to constant temperature for 3 minutes, and the pH was measured.
The table below shows the pH value of the stock solution of the liquid cleaning composition.
※２：洗浄性試験（デンプン汚れ）
＜被洗浄物＞
米デンプン汚れ（７．１％米デンプン水溶液を１００℃で１５分加熱したもの）を１５０×１５０ｍｍのガラスパネルにコーティングロッドを用いて均一に塗布し、室温で乾燥させたものを試験片とした。
＜試験方法＞
上記の方法で調整した試験片を、０．０５質量％に希釈した液体洗浄剤組成物の５Ｌ溶液中に５分間浸漬した。その後、以下の条件で自動食器洗浄機を用いた洗浄を行い、試験片を流水で軽くすすいだ後、室温にて乾燥させた。乾燥後、０．１質量％よう素液を試験片全体に振りかけ、よう素呈色した着色部分の割合を画像解析ソフトを用いて算出し、以下の基準で評価した。
*2: Cleanability test (starch stain)
<Object to be cleaned>
Rice starch stain (7.1% rice starch aqueous solution heated at 100°C for 15 minutes) was uniformly applied to a 150 x 150 mm glass panel using a coating rod, and the test piece was dried at room temperature. .
<Test method>
The test piece prepared by the above method was immersed for 5 minutes in a 5 L solution of a liquid cleaning composition diluted to 0.05% by mass. Thereafter, washing was performed using an automatic dishwasher under the following conditions, and the test piece was lightly rinsed with running water and then dried at room temperature. After drying, a 0.1% by mass iodine solution was sprinkled over the entire test piece, and the percentage of the colored part that developed iodine color was calculated using image analysis software, and evaluated based on the following criteria.
＜洗浄機条件＞
使用洗浄機：ＳＡＮＹＯ製自動食器洗浄機（ＤＷ－ＤＲ６２）
洗浄温度：６０℃
洗浄時間：４０秒
洗浄剤：ディッシュパワー（ＡＤＥＫＡクリーンエイド社製）
洗浄剤濃度：０．２質量％
使用水：炭酸カルシウム換算で、５０ｍｇ／Ｌ［ドイツ硬度２．８°ＤＨ］の硬水
＜評価基準＞
◎：洗浄率１００％～８０％以上
○：洗浄率８０％未満～６０％以上
△：洗浄率６０％未満～４０％以上
×：洗浄率４０％未満
とし、△、○、◎を実用性のあるものとして判定した。
<Washing machine conditions>
Washing machine used: SANYO automatic dishwasher (DW-DR62)
Washing temperature: 60℃
Cleaning time: 40 seconds Cleaning agent: Dish Power (manufactured by ADEKA Clean Aid)
Cleaning agent concentration: 0.2% by mass
Water used: Hard water of 50 mg/L [German hardness 2.8°DH] in terms of calcium carbonate <Evaluation criteria>
◎: Cleaning rate of 100% to 80% or more ○: Cleaning rate of less than 80% to 60% or more △: Cleaning rate of less than 60% to 40% or more ×: Cleaning rate of less than 40%, △, ○, and ◎ indicate practical It was determined that there was.
※３：洗浄性試験（タンパク質汚れ）
＜被洗浄物＞
５質量％の卵黄水溶液を１５０×１５０ｍｍのガラスパネルにコーティングロットを用いて均一に塗布し、室温で乾燥後、１００℃で３０秒間加温し、変性させたものを浄試験片とした。
＜試験方法＞
上記の方法で調整した試験片を、０．０５質量％に希釈した液体洗浄剤組成物の５Ｌ溶液中に５分間浸漬した。その後、以下の条件で自動食器洗浄機を用いた洗浄を行い、試験片を流水で軽くすすいだ後、室温にて乾燥させた。乾燥後、０．１質量％アミドブラック液を試験片全体に振りかけ、呈色した着色部分の割合を画像解析ソフトを用いて算出し、以下の基準で評価した。
*3: Cleanability test (protein stain)
<Object to be cleaned>
A 5% by mass egg yolk aqueous solution was uniformly applied to a 150 x 150 mm glass panel using a coating lot, and after drying at room temperature, it was heated at 100°C for 30 seconds to denature it and use it as a clean test piece.
<Test method>
The test piece prepared by the above method was immersed for 5 minutes in a 5 L solution of a liquid cleaning composition diluted to 0.05% by mass. Thereafter, washing was performed using an automatic dishwasher under the following conditions, and the test piece was lightly rinsed with running water and then dried at room temperature. After drying, 0.1% by mass amide black liquid was sprinkled over the entire test piece, the proportion of the colored part was calculated using image analysis software, and evaluated according to the following criteria.
＜洗浄機条件＞
使用洗浄機：ＳＡＮＹＯ製自動食器洗浄機（ＤＷ－ＤＲ６２）
洗浄温度：６０℃
洗浄時間：４０秒
洗浄剤：ディッシュパワー（ＡＤＥＫＡクリーンエイド社製）
洗浄剤濃度：０．２質量％
使用水：炭酸カルシウム換算で、５０ｍｇ／Ｌ［ドイツ硬度２．８°ＤＨ］の硬水
＜評価基準＞
◎：洗浄率１００％ ～７０％以上
○：洗浄率７０％未満～５５％以上
△：洗浄率５５％未満～４０％以上
×：洗浄率４０％未満
とし、△、○、◎を実用性のあるものとして判定した。
<Washing machine conditions>
Washing machine used: SANYO automatic dishwasher (DW-DR62)
Washing temperature: 60℃
Cleaning time: 40 seconds Cleaning agent: Dish Power (manufactured by ADEKA Clean Aid)
Cleaning agent concentration: 0.2% by mass
Water used: Hard water of 50 mg/L [German hardness 2.8°DH] in terms of calcium carbonate <Evaluation criteria>
◎: Cleaning rate 100% to 70% or more ○: Cleaning rate less than 70% to 55% or more △: Cleaning rate less than 55% to 40% or more ×: Cleaning rate less than 40%, and △, ○, and ◎ indicate practicality. It was determined that there was.
※４：原液の酵素安定性試験（アミラーゼ）
＜アミラーゼ活性測定＞
本試験では各液体洗浄剤組成物原液の、調整時と４０℃、３０日間保存後のアミラーゼ活性を測定した。各液体洗浄剤組成物原液は測定時に蒸留水で０．１質量％に希釈し、その希釈液０．０５ｍＬと０．１質量％可溶性デンプン水溶液０．５ｍＬとをｐＨ７．０、６０℃の条件下で１０分間反応させた後、ヨウ素試薬０．５ｍＬと蒸留水２ｍＬを添加した。分光光度計（ＳＨＩＭＡＤＺＵ ＵＶ－１８００）を用いて、得られた反応液の６２０ｎｍにおける吸光度を測定した。試料溶液１ｍＬが６０℃、１分間の反応でデンプンを分解する酵素の活力（アミラーゼ活性）を１単位として力価を求めた。液体洗浄剤組成物調整時のアミラーゼ活性を初期活性値として、４０℃、３０日間保存後の液体洗浄剤組成物のアミラーゼ活性の力価より、アミラーゼ活性の残存率を求めた。
＜評価基準＞
◎：初期活性値の９０％以上、１００％以下
○：初期活性値の７５％以上、９０％未満
△：初期活性値の５０％以上、７５％未満
×：初期活性値の０％以上、５０％未満
とし、△、○、◎を実用性のあるものとして判定した。
*4: Enzyme stability test of stock solution (amylase)
<Amylase activity measurement>
In this test, the amylase activity of each liquid detergent composition stock solution was measured at the time of preparation and after storage at 40° C. for 30 days. Each liquid detergent composition stock solution was diluted to 0.1% by mass with distilled water at the time of measurement, and 0.05mL of the diluted solution and 0.5mL of a 0.1% by mass soluble starch aqueous solution were mixed at pH 7.0 and at 60°C. After reacting for 10 minutes, 0.5 mL of iodine reagent and 2 mL of distilled water were added. The absorbance of the obtained reaction solution at 620 nm was measured using a spectrophotometer (SHIMADZU UV-1800). The titer was determined using the enzyme activity (amylase activity) that decomposes starch in a reaction of 1 mL of the sample solution at 60° C. for 1 minute as one unit. Using the amylase activity at the time of preparation of the liquid detergent composition as the initial activity value, the residual rate of amylase activity was determined from the amylase activity titer of the liquid detergent composition after storage at 40° C. for 30 days.
<Evaluation criteria>
◎: 90% or more of the initial activity value, 100% or less ○: 75% or more of the initial activity value, less than 90% △: 50% or more of the initial activity value, less than 75% ×: 0% or more of the initial activity value, 50 %, and △, ○, and ◎ were judged as being practical.
※５：希釈液の酵素安定性試験（アミラーゼ）
＜アミラーゼ活性測定＞
本試験では各液体洗浄剤組成物を０．１質量％に希釈した希釈液の、調整時と４０℃、６０分間保存後のアミラーゼ活性を測定した。各液体洗浄剤組成物の希釈液０．０５ｍＬと０．１質量％可溶性デンプン水溶液０．５ｍＬとをｐＨ７．０、６０℃の条件下で１０分間反応させた後、ヨウ素試薬０．５ｍＬと蒸留水２ｍＬを添加した。分光光度計（ＳＨＩＭＡＤＺＵ ＵＶ－１８００）を用いて、得られた反応液の６２０ｎｍにおける吸光度を測定した。試料溶液１ｍＬが６０℃、１分間の反応でデンプンを分解する酵素の活力（アミラーゼ活性）を１単位として力価を求めた。希釈液調整時のアミラーゼ活性を初期活性値として、４０℃、６０分間保存後の希釈液のアミラーゼ活性の力価より、アミラーゼ活性の残存率を求めた。
＜評価基準＞
◎：初期活性値の９０％以上、１００％以下
○：初期活性値の７５％以上、９０％未満
△：初期活性値の５０％以上、７５％未満
×：初期活性値の０％以上、５０％未満
とし、△、○、◎を実用性のあるものとして判定した。
*5: Enzyme stability test of diluted solution (amylase)
<Amylase activity measurement>
In this test, the amylase activity of each liquid detergent composition diluted to 0.1% by mass was measured during preparation and after storage at 40° C. for 60 minutes. After reacting 0.05 mL of the diluted solution of each liquid detergent composition with 0.5 mL of 0.1% by mass soluble starch aqueous solution for 10 minutes at pH 7.0 and 60°C, the mixture was distilled with 0.5 mL of iodine reagent. 2 mL of water was added. The absorbance of the obtained reaction solution at 620 nm was measured using a spectrophotometer (SHIMADZU UV-1800). The titer was determined using the enzyme activity (amylase activity) that decomposes starch in a reaction of 1 mL of the sample solution at 60° C. for 1 minute as one unit. The residual rate of amylase activity was determined from the amylase activity titer of the diluted solution after storage at 40° C. for 60 minutes, using the amylase activity at the time of preparing the diluted solution as the initial activity value.
<Evaluation criteria>
◎: 90% or more of the initial activity value, 100% or less ○: 75% or more of the initial activity value, less than 90% △: 50% or more of the initial activity value, less than 75% ×: 0% or more of the initial activity value, 50 %, and △, ○, and ◎ were judged as being practical.
※６：原液の酵素安定性試験（プロテアーゼ）
＜プロテアーゼ活性測定＞
本試験では各液体洗浄剤組成物原液の、調整時と４０℃、３０日間保存後のプロテアーゼ活性を測定した。各液体洗浄剤組成物原液は測定時にｐＨ７．０の酢酸緩衝液で０．１質量％に希釈し、その希釈液０．２ｍＬと０．６質量％カゼイン水溶液１ｍＬとをｐＨ７．０、６０℃の条件下で１０分間反応させた後、タンパク質沈殿試薬（ＴＣＡ混液）１ｍＬを添加して３０℃で３０分間放置した。放置後、得られた水溶液をろ過し、このろ液１ｍＬに０．５５ＭのＮａ２ＣＯ３水溶液２．５ｍＬ、および蒸留水で３倍希釈したＦｏｌｉｎ試薬０．５ｍＬを添加し３０℃、３０分間反応させた。分光光度計（ＳＨＩＭＡＤＺＵ ＵＶ－１８００）を用いて、得られた反応液の６６０ｎｍにおける吸光度を測定し、６０℃、１分間にこの反応液全体で１γのＬ－チロジンの呈するＦｏｌｉｎ呈色度を与えるプロテアーゼ活性を１単位として力価を求めた。液体洗浄剤組成物調整時のプロテアーゼ活性を初期活性値として、４０℃、３０日間保存後の液体洗浄剤組成物のプロテアーゼ活性の力価より、プロテアーゼ活性の残存率を求めた。
＜評価基準＞
◎：初期活性値の９０％以上、１００％以下
○：初期活性値の７５％以上、９０％未満
△：初期活性値の５０％以上、７５％未満
×：初期活性値の０％以上、５０％未満
とし、△、○、◎を実用性のあるものとして判定した。
*6: Enzyme stability test of stock solution (protease)
<Protease activity measurement>
In this test, the protease activity of each liquid detergent composition stock solution was measured at the time of preparation and after storage at 40° C. for 30 days. Each liquid detergent composition stock solution was diluted to 0.1% by mass with an acetate buffer of pH 7.0 at the time of measurement, and 0.2 mL of the diluted solution and 1 mL of a 0.6% by mass casein aqueous solution were mixed at pH 7.0 at 60°C. After reacting for 10 minutes under these conditions, 1 mL of protein precipitation reagent (TCA mixture) was added and left at 30°C for 30 minutes. After standing, the resulting aqueous solution was filtered, and 2.5 mL of 0.55 M Na 2 CO 3 aqueous solution and 0.5 mL of Folin's reagent diluted 3 times with distilled water were added to 1 mL of this filtrate at 30° C. for 30 minutes. Made it react. Using a spectrophotometer (SHIMADZU UV-1800), measure the absorbance of the obtained reaction solution at 660 nm, and give the entire reaction solution the Folin coloration exhibited by 1γ L-tyrosine in 1 minute at 60°C. The titer was determined using protease activity as one unit. Using the protease activity at the time of preparation of the liquid detergent composition as the initial activity value, the residual rate of protease activity was determined from the protease activity titer of the liquid detergent composition after storage at 40° C. for 30 days.
<Evaluation criteria>
◎: 90% or more of the initial activity value, 100% or less ○: 75% or more of the initial activity value, less than 90% △: 50% or more of the initial activity value, less than 75% ×: 0% or more of the initial activity value, 50 %, and △, ○, and ◎ were judged as being practical.
※７：希釈液の酵素安定性試験（プロテアーゼ）
＜プロテアーゼ活性測定＞
本試験では各液体洗浄剤組成物を０．１質量％に希釈した希釈液の、調整時と４０℃、６０分間保存後のプロテアーゼ活性を測定した。各液体洗浄剤組成物の希釈液０．２ｍＬと０．６質量％カゼイン水溶液１ｍＬとをｐＨ７．０、６０℃の条件下で１０分間反応させた後、タンパク質沈殿試薬（ＴＣＡ混液）１ｍＬを添加して３０℃で３０分間放置した。放置後、得られた水溶液をろ過し、このろ液１ｍＬに０．５５ＭのＮａ２ＣＯ３水溶液２．５ｍＬ、および蒸留水で３倍希釈したＦｏｌｉｎ試薬０．５ｍＬを添加し３０℃、３０分間反応させた。分光光度計（ＳＨＩＭＡＤＺＵ ＵＶ－１８００）を用いて、得られた反応液の６６０ｎｍにおける吸光度を測定し、６０℃、１分間にこの反応液全体で１γのＬ－チロジンの呈するＦｏｌｉｎ呈色度を与えるプロテアーゼ活性を１単位として力価を求めた。希釈液調整時のプロテアーゼ活性を初期活性値として、４０℃、６０分間保存後の希釈液のプロテアーゼ活性の力価より、プロテアーゼ活性の残存率を求めた。
*7: Enzyme stability test of diluted solution (protease)
<Protease activity measurement>
In this test, the protease activity of a diluted solution obtained by diluting each liquid detergent composition to 0.1% by mass was measured at the time of preparation and after storage at 40° C. for 60 minutes. After reacting 0.2 mL of each liquid detergent composition diluted solution with 1 mL of 0.6 mass% casein aqueous solution for 10 minutes at pH 7.0 and 60°C, 1 mL of protein precipitation reagent (TCA mixture) was added. The mixture was left at 30°C for 30 minutes. After standing, the resulting aqueous solution was filtered, and 2.5 mL of 0.55 M Na 2 CO 3 aqueous solution and 0.5 mL of Folin's reagent diluted 3 times with distilled water were added to 1 mL of this filtrate at 30° C. for 30 minutes. Made it react. Using a spectrophotometer (SHIMADZU UV-1800), measure the absorbance of the obtained reaction solution at 660 nm, and give the entire reaction solution the Folin coloration exhibited by 1γ L-tyrosine in 1 minute at 60°C. The titer was determined using protease activity as one unit. Using the protease activity at the time of preparing the diluted solution as the initial activity value, the residual rate of protease activity was determined from the protease activity titer of the diluted solution after storage at 40° C. for 60 minutes.
※８：貯蔵安定性試験
試験方法：
各液体洗浄剤組成物１００ｇをポリプロピレン製容器に入れ、－５℃、２５℃、４０℃で１ヶ月静置した後に外観を観察し、以下の基準で評価した。
評価基準：
○：分離や濁りが見られず安定である
△：全体的な分離はないが、若干の濁りが見られる
×：分離もしくは濁りが見られる
とし、△、○を実用性のあるものとして判定した。
*8: Storage stability test method:
100 g of each liquid cleaning composition was placed in a polypropylene container and allowed to stand for one month at -5°C, 25°C, and 40°C, and then its appearance was observed and evaluated using the following criteria.
Evaluation criteria:
○: Stable with no separation or turbidity △: No overall separation, but some turbidity ×: Separation or turbidity observed, and △ and ○ were judged as practical. .
※９：洗浄性試験（油脂汚れ）
＜被洗浄物＞
米デンプン水溶液（２０質量％米デンプン水溶液を８０℃で３分加熱したもの）に、１００℃で加熱し溶解した牛脂２０ｇを加えよく攪拌し５３℃まで冷ました後、卵黄１０ｇを加えて攪拌したものを汚れとした。この汚れを１５ｃｍ×１５ｃｍの塩化ビニル製の黒色プレートに、コーティングロッドを用いて均一に塗布し、室温で乾燥させて試験片とした。
＜試験方法＞
上記の方法で調整した試験片１枚を洗浄ラックに設置し、以下に記載の洗浄条件にて洗浄後、流水で軽くすすいだ。洗浄すすぎ後の試験片の汚れ残留部分を５ｍｍ四方の碁盤目上にスケッチし、清浄な碁盤目を数え、その清浄面積率を洗浄率とし、以下の基準で評価した。
*9: Cleanability test (oil stains)
<Object to be cleaned>
To a rice starch aqueous solution (a 20% by mass rice starch aqueous solution heated at 80°C for 3 minutes), 20g of beef tallow heated and dissolved at 100°C was added, stirred well, cooled to 53°C, and then 10g of egg yolk was added and stirred. Made things dirty. This stain was uniformly applied to a 15 cm x 15 cm black plate made of vinyl chloride using a coating rod, and dried at room temperature to obtain a test piece.
<Test method>
One test piece prepared by the above method was placed on a washing rack, washed under the washing conditions described below, and then lightly rinsed with running water. After cleaning and rinsing, the remaining dirt portion of the test piece was sketched on a 5 mm square grid, the clean grid was counted, and the clean area ratio was defined as the cleaning rate, and evaluated based on the following criteria.
＜洗浄条件＞
使用洗浄機：ホシザキ製自動食器洗浄機（機種ＪＷＥ－６８０）
洗浄温度：６４℃
洗浄時間：４０秒
洗浄剤濃度：０．０７質量％
使用水：炭酸カルシウム換算で、５０ｍｇ／Ｌ［ドイツ硬度２．８°ＤＨ］の硬水
＜評価基準＞
◎：洗浄率が５０％以上、１００％以下
○：洗浄率が３０％以上、５０％未満
△：洗浄率が１０％以上、３０％未満
×：洗浄率が０％以上、１０％未満
とし、△、○、◎を実用性のあるものとして判定した。
<Cleaning conditions>
Washing machine used: Hoshizaki automatic dishwasher (model JWE-680)
Washing temperature: 64℃
Cleaning time: 40 seconds Cleaning agent concentration: 0.07% by mass
Water used: Hard water of 50 mg/L [German hardness 2.8°DH] in terms of calcium carbonate <Evaluation criteria>
◎: Cleaning rate is 50% or more and 100% or less ○: Cleaning rate is 30% or more and less than 50% △: Cleaning rate is 10% or more and less than 30% ×: Cleaning rate is 0% or more and less than 10%, △, ◎, and ◎ were judged as having practicality.
即ち本発明は、
液体洗浄剤組成物であって、
（１）（Ａ）成分として、クメンスルホン酸ナトリウム、キシレンスルホン酸ナトリウム及びパラトルエンスルホン酸ナトリウムからなる群より選択される少なくとも一種を液体洗浄剤組成物全量に対して０．１～７．５質量％、
（Ｂ）成分として、チオ硫酸ナトリウム及びチオ硫酸カリウムからなる群より選択される少なくとも一種を液体洗浄剤組成物全量に対して０．００８～０．８質量％、
（Ｃ）成分として、プロピレングリコール、へキシレングリコール及びグリセリンからなる群より選択される少なくとも一種、
（Ｄ）成分としてアミラーゼ、
（Ｅ）成分としてプロテアーゼ、
（Ｆ）成分として水、
を含有し、（Ａ）成分と（Ｂ）成分の質量比（Ａ）／（Ｂ）の値が４以上、１０００以下であり、組成物の２５℃におけるｐＨが６以上、８以下であり、自動食器洗浄機用洗浄剤又は食器の浸漬用洗浄剤として用いられる液体洗浄剤組成物、
（２）さらに、（Ｇ）成分としてギ酸又はそのアルカリ金属塩、塩化カルシウム、酢酸カルシウム、及びグリシンからなる群より選択される少なくとも一種以上の酵素安定化剤を含有する、（１）の液体洗浄剤組成物、
（３）さらに、（Ｈ）成分として下記の一般式（１）で表されるノニオン界面活性剤を含有する、（１）又は（２）の液体洗浄剤組成物である。
That is, the present invention
A liquid cleaning composition comprising:
(1) As component (A), at least one selected from the group consisting of sodium cumene sulfonate, sodium xylene sulfonate, and sodium paratoluene sulfonate is added at a rate of 0.1 to 7.5 based on the total amount of the liquid cleaning composition. Mass% ,
As component (B) , at least one selected from the group consisting of sodium thiosulfate and potassium thiosulfate is contained in an amount of 0.008 to 0.8% by mass based on the total amount of the liquid cleaning composition;
(C) As a component , at least one member selected from the group consisting of propylene glycol, hexylene glycol, and glycerin ;
(D) amylase as a component;
(E) protease as a component;
(F) water as a component;
, the mass ratio (A)/(B) of component (A) and component (B) is 4 or more and 1000 or less, and the pH of the composition at 25°C is 6 or more and 8 or less. , a liquid cleaning composition used as a cleaning agent for automatic dishwashers or a cleaning agent for dipping dishes ,
( 2 ) The liquid cleaning of (1) further contains as component (G) at least one enzyme stabilizer selected from the group consisting of formic acid or its alkali metal salt, calcium chloride, calcium acetate, and glycine. agent composition,
( 3 ) The liquid cleaning composition of (1) or (2) further contains a nonionic surfactant represented by the following general formula (1) as the (H) component.
（式中、Ｒは、炭素数８以上、１６以下のアルキル基を表し、ｍは、２以上、１０以下の数を表し、ｎは、０以上、１０以下の数を表し、ｍ≧ｎである。） (In the formula, R represents an alkyl group having 8 or more and 16 or less carbon atoms, m represents a number of 2 or more and 10 or less, n represents a number of 0 or more and 10 or less, and m≧n There is. )
実施例１～４０、比較例１～１０
表１～表５に示す液体洗浄剤組成物を調製した。各液体洗浄剤組成物を用いて、ｐＨ、洗浄性、酵素安定性、貯蔵安定性を測定した。表１～４に実施例１～４０の結果を、表５に比較例１～１０の結果をそれぞれ示す。
なお、実施例１０は参考例である。
Examples 1 to 40, Comparative Examples 1 to 10
Liquid cleaning compositions shown in Tables 1 to 5 were prepared. Using each liquid detergent composition, pH, detergency, enzyme stability, and storage stability were measured. Tables 1 to 4 show the results of Examples 1 to 40, and Table 5 shows the results of Comparative Examples 1 to 10, respectively.
Note that Example 10 is a reference example.
Claims (6)
（Ｂ）成分としてチオ硫酸又はその塩、及び亜硫酸又はその塩からなる群より選択される少なくとも一種、
（Ｃ）成分として多価アルコール、
（Ｄ）成分としてアミラーゼ、
（Ｅ）成分としてプロテアーゼ、
（Ｆ）成分として水、
を含有し、（Ａ）成分と（Ｂ）成分の質量比（Ａ）／（Ｂ）の値が４以上、１０００以下であり、組成物の２５℃におけるｐＨが６以上、８以下である液体洗浄剤組成物。 (A) As a component, an aromatic sulfonic acid or a salt thereof;
(B) At least one member selected from the group consisting of thiosulfuric acid or its salt, and sulfite or its salt,
(C) polyhydric alcohol as a component;
(D) amylase as a component;
(E) protease as a component;
(F) water as a component;
, the mass ratio (A)/(B) of component (A) and component (B) is 4 or more and 1000 or less, and the pH of the composition at 25°C is 6 or more and 8 or less. Cleaning composition.
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|---|---|---|---|---|
| JP2002294284A (en) * | 2001-03-28 | 2002-10-09 | Kao Corp | Liquid detergent composition for clothes |
| JP2003073698A (en) * | 2001-08-30 | 2003-03-12 | Kao Corp | Detergent composition for coating fabric |
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| JP2016160279A (en) * | 2015-02-26 | 2016-09-05 | 花王株式会社 | Liquid detergent article |
| JP2018115286A (en) * | 2017-01-20 | 2018-07-26 | 株式会社Adeka | Neutral detergent composition |
| WO2020070011A1 (en) * | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition |
| JP2020084141A (en) * | 2018-11-30 | 2020-06-04 | ライオン株式会社 | Liquid detergent composition for fiber product |
| JP2020152760A (en) * | 2019-03-18 | 2020-09-24 | ライオン株式会社 | Method for producing liquid detergent composition |
| JP2020176264A (en) * | 2019-04-22 | 2020-10-29 | ライオン株式会社 | Liquid detergent composition for textile products |
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294284A (en) * | 2001-03-28 | 2002-10-09 | Kao Corp | Liquid detergent composition for clothes |
| JP2003073698A (en) * | 2001-08-30 | 2003-03-12 | Kao Corp | Detergent composition for coating fabric |
| JP2005255915A (en) * | 2004-03-12 | 2005-09-22 | Nippon Shokubai Co Ltd | Additive for liquid detergent |
| JP2016160279A (en) * | 2015-02-26 | 2016-09-05 | 花王株式会社 | Liquid detergent article |
| JP2018115286A (en) * | 2017-01-20 | 2018-07-26 | 株式会社Adeka | Neutral detergent composition |
| WO2020070011A1 (en) * | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition |
| JP2020084141A (en) * | 2018-11-30 | 2020-06-04 | ライオン株式会社 | Liquid detergent composition for fiber product |
| JP2020152760A (en) * | 2019-03-18 | 2020-09-24 | ライオン株式会社 | Method for producing liquid detergent composition |
| JP2020176264A (en) * | 2019-04-22 | 2020-10-29 | ライオン株式会社 | Liquid detergent composition for textile products |
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